EP0284289B1 - Zusammensetzung aus Polyurethanharz - Google Patents

Zusammensetzung aus Polyurethanharz Download PDF

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Publication number
EP0284289B1
EP0284289B1 EP88302323A EP88302323A EP0284289B1 EP 0284289 B1 EP0284289 B1 EP 0284289B1 EP 88302323 A EP88302323 A EP 88302323A EP 88302323 A EP88302323 A EP 88302323A EP 0284289 B1 EP0284289 B1 EP 0284289B1
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EP
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Prior art keywords
tetrahydrofuran
alkyl
hydrogen atom
polyurethane resin
resin composition
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Expired - Lifetime
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EP88302323A
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English (en)
French (fr)
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EP0284289A3 (en
EP0284289A2 (de
Inventor
Kazuaki Okabe
Hideyuki Ishii
Haruo Watanabe
Shuichi Takeuchi
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Hodogaya Chemical Co Ltd
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Hodogaya Chemical Co Ltd
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Publication of EP0284289A2 publication Critical patent/EP0284289A2/de
Publication of EP0284289A3 publication Critical patent/EP0284289A3/en
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Publication of EP0284289B1 publication Critical patent/EP0284289B1/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4858—Polyethers containing oxyalkylene groups having more than four carbon atoms in the alkylene group

Definitions

  • the present invention relates to a polyurethane resin composition.
  • Polyethers are widely used as soft segment components of polyurethane resins, and among them, polytetramethylene ether glycols are especially noticed as the soft segment component because of their furnishing polyurethane resins with superior elastic characteristics, low-temperature characteristics and hydrolytic resistance.
  • the polytetramethylene ether glycols, polymers of tetrahydrofuran (“THF”), usable for polyurethane resins have molecular weights of 500-4000 and melting points of 20-40°C. Accordingly, they crystallize at room temperature or lower, and thus have problems not only in handling and workability but also in the application fields of painting, coating and sealing where curing at room temperature is required. Hitherto in these fields, suitable organic solvents have been added to repress the crystallization, however, non-solvent type polyurethane resins have recently been intended for preventing environmental pollution and rationalization. Under the circumstances, it has been desired for the polytetramethylene ether glycol to improve the problem of crystallization with simultaneous maintenance of the superior characteristics.
  • THF tetrahydrofuran
  • THF/propylene oxide copolyether polyol As an approach to improve the defect of the polytetramethylene ether glycol, a THF/propylene oxide copolyether polyol has been known [Journal of Polymer Science, 58 , 857-863 (1962)].
  • this polyol is a copolymer of THF with propylene oxide and so its terminal group is a secondary hydroxyl group like that of the polypropyleneoxide polyol, it is low in reactivity with an isocyanate group, and besides the resulting polyurethanes are not so superior in their properties.
  • this polyol is a still unsatisfactory one, although it is low in the crystallizability and keeps liquid state at room temperature.
  • the 3-alkyl substituted tetrahydrofuran used in the present invention is represented by the following general formula; wherein one of R1 and R2 is hydrogen atom and another is an alkyl group of 1-4 carbon atoms.
  • 3-alkyl substituted tetrahydrofuran is 3-methyl THF, which can be synthesized by hydroformylation of 1,4-butenediol and subsequent hydrogenation thereof or reduction of itaconic acid, as disclosed in U.S. Patent No. 3,859,369 (Copelin).
  • the copolyether polyol in the present invention is obtained by copolymerization of THF and a 3-alkyl THF, for example, 3-methyl THF, at a molar ratio of 85/15 - 20/80 in the presence of a strong acid capable of causing ring-opening of THF such as, for example, chlorosulfonic acid, fluorosulfonic or perchloric acid normally at a temperature of 0°C - 50°C.
  • This copolyether polyol has a melting point of about 10°C or lower and maintains completely liquid state at room temperature.
  • the mixing molar ratio When the mixing molar ratio is smaller than 20/80, the copolyether shows substantially no melting point and abrupt high glass transition point, so that the polyol is not desired for low-temperature characteristics of polyurethane resins.
  • the mixing molar ratio is larger than 85/15, the crystallizability increases due to the increase in melting point and this does not achieve the object.
  • the mixing molar ratio of THF/3-methyl THF for obtaining preferred copolyether polyols are settled at 80/20 - 30/70, preferably.
  • the copolyether polyol is a colorless and transparent liquid at room temperature, and since it has a primary hydroxyl group as the terminal group, the reactivity with isocyanate group is about 3-4 times as high as that of a polypropyleneoxide polyol or a THF/propylene oxide copolyether polyol. Therefore, this copolyether polyol is suitable especially in use for room temperature curing process and further reaction injection molding (RIM) process in the field of polyurethane resins.
  • RIM reaction injection molding
  • Molecular weight of the copolyether polyol used in the present invention is 500-5000, and especially polyols of 800-4500 can exhibit conspicuous effects of the present invention.
  • Polyisocyanate compounds usable for the present invention are those which contain at least two isocyanate groups in the molecule, and as examples thereof, mention may be made of polyisocyanate compounds generally used for synthesis of polyurethane resins such as tolylene diisocyanate (TDI), 4,4 ⁇ -diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, naphthylene diisocyanate and hydrogenated diphenylmethane diisocyanate. These are used alone or in combination of two or more.
  • TDI tolylene diisocyanate
  • MDI 4,4 ⁇ -diphenylmethane diisocyanate
  • hexamethylene diisocyanate xylylene diisocyanate
  • isophorone diisocyanate naphthylene diisocyanate
  • hydrogenated diphenylmethane diisocyanate are
  • the active hydrogen atom-containing compounds reactive with isocyanate group are ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, xylylene glycol, glycerin, trimethylolpropane, ethylenediamine, propylenediamine, phenylenediamine, diaminodiphenylmethane, methylene bis(2-chloroaniline), hydrazine compounds and water.
  • Resins obtained by using diamines, hydrazines or water are polyurethane-ureas.
  • Polyurethane resin compositions of the present invention may be obtained by such ordinary processes for production of polyurethane resins as by the two-stage process which comprise reacting the copolyether polyol with the polyisocyanate compound to synthesize an isocyanate group-containing prepolymer and then reacting the prepolymer with the active hydrogen atom-containing compound, and by the one-shot process which comprises reacting simultaneously the copolyether polyol, the polyisocyanate and the active hydrogen atom-containing compound.
  • the reaction temperature varies depending on process and use of the product, but generally it is carried out at 50-200°C. In the present invention, the reaction may also be effected at lower than 50°C because melting point of the copolyether polyol is low.
  • compositional ratio of the components varies depending on the objective polyurethane resins, but the prepolymer must contain isocyanate group, and the isocyanate group in the polyisocyanate prepolymer is 1 or more, preferably 1.2 or more equivalent per 1 equivalent of hydroxyl group of the copolyether polyol.
  • Compositional ratio of the final reactants, urethane resins is that the total equivalent of active hydrogen atom contained in the copolyether polyol and in the chain extender is 0.9-1.1 per 1 equivalent of isocyanate group.
  • catalysts include, for example, triethylamine, tributylamine, dibutyl tin dilaurate and stannous octylate and the stabilizers include, for example, ionol (BHT), distearyl thiodipropionate, di- ⁇ -naphthylphenylenediamine and tri(dinonylphenyl)phosphite.
  • BHT ionol
  • distearyl thiodipropionate di- ⁇ -naphthylphenylenediamine
  • tri(dinonylphenyl)phosphite tri(dinonylphenyl)phosphite
  • polyurethane resins of the present invention are excellent elastic materials which are much superior in properties to polyurethane resins obtained with polypropyleneoxide polyols or THF/propylene oxide copolyether polyols which are liquid at room temperature, and they are nearly the same in properties as polyurethanes obtained with polytetramethylene ether polyols.
  • hydroxyl number (OH value; mg KOH/g) of the copolyether polyol was obtained by the pyridine-acetic anhydride method, from which the number-average molecular weight was obtained.
  • Compositional analysis and terminal hydroxyl group analysis of 3-methyl THF unit and THF unit were conducted by 13C-NMR (FX-60 manufactured by Nihon Denshi Co.), and melting point (Tm) and glass transition point (Tg) were measured by DSC (DSC-8230 manufactured by Rigaku Denki Co.). Properties of polyurethane were measured in accordance with JIS-K6301.
  • thermometer In a one liter four-necked separable flask provided with a stirrer, a thermometer and an N2 seal device were charged 288.4 g (4 mols) of dehydrated THF and 86.1 g (1 mol) of 3-methyl THF at a mixing molar ratio of 80/20 and thereto were added 10.5 g of 70% perchloric acid and 95 g of acetic anhydride at 10°C. Polymerization reaction was effected for 8 hours.
  • Copolyether glycols and polyurethanes were prepared in the same manner as in Example 1 except that the mixing molar ratio of THF and 3-methyl THF was 50/50 (Example 2), 30/70 (Example 3), 90/10 (Comparative Example 1), 10/90 (Comparative Example 2) or 80/20 (molecular weight 2000, Example 4) and amount of perchloric acid/acetic anhydride was changed depending on the desired molecular weights. Properties of the resulting copolyether glycol and polyurethane are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (12)

  1. Polyurethanharzmasse, umfassend ein Copolyetherpolyol eines Molekulargewichts von 500 bis 5000, erhalten durch Copolymerisation von Tetrahydrofuran und eines 3-Alkyl-tetrahydrofurans in einem molaren Mischungsverhältnis von 85/15 bis 20/80, eine Polyisocyanatverbindung und eine ein aktives Wasserstoffatom aufweisende Verbindung in Form von Ethylenglykol, Propylenglykol, 1,4-Butandiol, 1,6-Hexandiol, Xylylenglykol, Gylzerin, Trimethylolpropan, Ethylendiamin, Propylendiamin, Phenylendiamin, Diaminodiphenylmethan, Methylen-bis(2-chloranilin), einer Hydrazinverbindung oder von Wasser.
  2. Polyurethanharzmasse nach Anspruch 1, wobei das 3-Alkyltetrahydrofuran durch die Formel:
    Figure imgb0006
        worin einer der Reste R₁ und R₂ für ein Wasserstoffatom steht und der andere eine Alkylgruppe mit 1 bis 4 Kohlenstoffatom(en) darstellt, wiedergegeben wird.
  3. Polyurethanharzmasse nach Anspruch 1, wobei das 3-Alkyltetrahydrofuran aus 3-Methyltetrahydrofuran besteht.
  4. Polyurethanharzmasse nach Anspruch 1, wobei die Mischpolymerisation von Tetrahydrofuran und 3-Alkyltetrahydrofuran in Gegenwart eines starken Säurekatalysators durchgeführt wird.
  5. Polyurethanharzmasse nach Anspruch 1, wobei die das aktive Wasserstoffatom aufweisende Verbindung mindestens 2 Hydroxylgruppen oder Aminogruppen aufweist.
  6. Verfahren zur Herstellung eines Polyurethanharzes durch Umsetzen eines Copolyetherpolyols eines Molekulargewichts von 500 bis 5000, erhalten durch Copolymerisation von Tetrahydrofuran und eines 3-Alkyltetrahydrofurans in einem molaren Mischungsverhältnis von 85/15 bis 20/80, einer Polyisocyanatverbindung und einer ein aktives Wasserstoffatom aufweisenden Verbindung in Form von Ethylenglykol, Propylenglykol, 1,4-Butandiol, 1,6-Hexandiol, Xylylenglykol, Glyzerin, Trimethylolpropan, Ethylendiamin, Propylendiamin, Phenylendiamin, Diaminodiphenylmethan, Methylenbis(2-chloranilin), einer Hydrazinverbindung oder von Wasser.
  7. Verfahren nach Anspruch 6, wobei das 3-Alkyltetrahydrofuran durch die Formel:
    Figure imgb0007
        worin einer der Reste R₁ und R₂ für ein Wasserstoff-atom steht und der andere eine Alkylgruppe mit 1 bis 4 Kohlenstoffatom(en) darstellt, wiedergegeben wird.
  8. Verfahren nach Anpruch 6, wobei das 3-Alkyltetrahydrofuran aus 3-Methyltetrahydrofuran besteht.
  9. Verfahren nach Anspruch 6, wobei die Mischpolymerisation von Tetrahydrofuran und 3-Alkyltetrahydrofuran in Gegenwart eines starken Säurekatalysators durchgeführt wird.
  10. Verfahren nach Anspruch 6, wobei die das aktive Wasserstoffatom aufweisende Verbindung mindestens 2 Hydroxylgruppen oder Aminogruppen aufweist.
  11. Verfahren nach Anspruch 6, wobei das Copolyetherpolyol mit dem Polyisocyanat zu einem isocyanatgruppenhaltigen Prepolymeren umgesetzt und danach das Prepolymere mit der ein aktives Wasserstoffatom aufweisenden Verbindung reagieren gelassen wird.
  12. Verfahren nach Anspruch 6, wobei das Copolyetherpolyol, die Polyisocyanatverbindung und die ein aktives Wasserstoffatom aufweisende Verbindung gleichzeitig umgesetzt werden.
EP88302323A 1987-03-25 1988-03-17 Zusammensetzung aus Polyurethanharz Expired - Lifetime EP0284289B1 (de)

Applications Claiming Priority (2)

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JP62068764A JPH07116276B2 (ja) 1987-03-25 1987-03-25 ポリウレタン樹脂の製造方法
JP68764/87 1987-03-25

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EP0284289A2 EP0284289A2 (de) 1988-09-28
EP0284289A3 EP0284289A3 (en) 1990-01-10
EP0284289B1 true EP0284289B1 (de) 1993-01-07

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EP (1) EP0284289B1 (de)
JP (1) JPH07116276B2 (de)
DE (1) DE3877231T2 (de)

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JP4905132B2 (ja) 2004-10-20 2012-03-28 旭硝子株式会社 ウレタン樹脂溶液、その製造方法及びウレタン樹脂の製造方法
CN101039981B (zh) * 2004-10-21 2010-09-08 旭硝子株式会社 聚氨酯树脂及聚氨酯树脂溶液的制造方法
CN101542345B (zh) 2006-11-27 2011-12-28 大自达电线株式会社 防蝉用引入光缆
JP5436190B2 (ja) * 2009-12-17 2014-03-05 三菱電機株式会社 エレベータ用ロープ
JP5797697B2 (ja) * 2012-07-30 2015-10-21 三洋化成工業株式会社 ポリウレタン樹脂
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CN110603281B (zh) 2017-05-30 2022-12-13 保土谷化学工业株式会社 生物聚醚多元醇的制备方法、生物聚醚多元醇及生物聚氨酯树脂
JP7166854B2 (ja) 2017-09-27 2022-11-08 キヤノン株式会社 電子写真用部材、プロセスカートリッジ及び電子写真装置

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Also Published As

Publication number Publication date
DE3877231T2 (de) 1993-05-06
US4960849A (en) 1990-10-02
DE3877231D1 (de) 1993-02-18
JPS63235320A (ja) 1988-09-30
EP0284289A3 (en) 1990-01-10
EP0284289A2 (de) 1988-09-28
JPH07116276B2 (ja) 1995-12-13

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